Photochemical reaction kinetics and mechanistic investigations of nitrous acid with sulfamethazine in tropospheric water

Nitrous acid (HONO) is an important atmospheric pollutant that can strongly absorb ultraviolet irradiation in the region of 300–400 nm, as previously reported. Since the solar irradiance that reaches the surface of the earth has wavelengths greater than 290 nm, the photodissociation of HONO is considered the major method of hydroxyl radical formation in the troposphere. Thus, the photoinduced chemical reactivity of HONO is important. The present work investigated the reaction mechanism and kinetic parameters of HONO and sulfamethazine by using a laser flash photolysis technique and liquid chromatography-mass spectrometry. The results indicated that the sulfamethazine degradation rate was influenced by the HONO concentration and the initial concentration of sulfamethazine. Hydroxyl radicals derived from the photolysis of HONO attacked the aromatic ring of sulfamethazine to form sulfamethazine-OH adducts with a second-order rate constant of (3.8 ± 0.3) × 109 L mol−1 s−1. This intermediate would then react with HO· and oxygen molecules. The reaction rate constants of sulfamethazine-OH adducts with oxygen are (1.3 ± 0.1) × 107 L mol−1 s−1. The generation of sulfanilic acid and pyrimidine implies that the breaking down of S–N bonds of sulfamethazine and its HO adducts probably occur at the same time.